EP0684978B1 - Lubricant composition containing alkoxylated amine salts of acids - Google Patents
Lubricant composition containing alkoxylated amine salts of acids Download PDFInfo
- Publication number
- EP0684978B1 EP0684978B1 EP94909034A EP94909034A EP0684978B1 EP 0684978 B1 EP0684978 B1 EP 0684978B1 EP 94909034 A EP94909034 A EP 94909034A EP 94909034 A EP94909034 A EP 94909034A EP 0684978 B1 EP0684978 B1 EP 0684978B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- composition
- carbon atoms
- derived
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000002253 acid Substances 0.000 title claims abstract description 81
- -1 amine salts Chemical class 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000000314 lubricant Substances 0.000 title abstract description 14
- 150000007513 acids Chemical class 0.000 title description 19
- 239000003921 oil Substances 0.000 claims abstract description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 32
- 239000010687 lubricating oil Substances 0.000 claims abstract description 32
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002485 combustion reaction Methods 0.000 claims abstract description 16
- 230000001603 reducing effect Effects 0.000 claims abstract description 7
- 239000000446 fuel Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 43
- 150000001412 amines Chemical class 0.000 description 22
- 239000000654 additive Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 10
- 125000002723 alicyclic group Chemical group 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 238000005461 lubrication Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 5
- 239000010689 synthetic lubricating oil Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- ZUNYMXPJGBXUCI-UHFFFAOYSA-N dioctoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCOP(S)(=S)OCCCCCCCC ZUNYMXPJGBXUCI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000008054 sulfonate salts Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- HHXCMCNHNPGJNS-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzenecarbodithioic acid Chemical compound CC(C)(C)C1=CC(C(S)=S)=CC(C(C)(C)C)=C1O HHXCMCNHNPGJNS-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- AAIUWVOMXTVLRG-UHFFFAOYSA-N 8,8-dimethylnonan-1-amine Chemical compound CC(C)(C)CCCCCCCN AAIUWVOMXTVLRG-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- BOFZOTMTKBQRAB-UHFFFAOYSA-N azanium;2-carboxyphenolate Chemical compound N.OC(=O)C1=CC=CC=C1O BOFZOTMTKBQRAB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940056345 tums Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
- C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/16—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiourea type, i.e. containing the group
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
- C10M137/105—Thio derivatives not containing metal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/064—Thiourea type compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/09—Heterocyclic compounds containing no sulfur, selenium or tellurium compounds in the ring
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/12—Gas-turbines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/12—Gas-turbines
- C10N2040/13—Aircraft turbines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/135—Steam engines or turbines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol-fuelled engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
- C10N2040/253—Small diesel engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/26—Two-strokes or two-cycle engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Definitions
- This invention relates to lubricant compositions containing alkoxylated amine salts of hydrocarbylsalicylic acids, trithiocyanuric acid, hydrocarbylsulfonic acids, dihydrocarbyldithiophosphoric acids or dihydrocarbyldithiobenzoic acids and to the use of such salts to reduce friction and/or improve fuel economy in an internal combustion engine.
- ZDDP zinc dialkyldithiophosphate
- U.S. Patent 4,575,431 discloses a lubricating oil additive composition containing dihydrocarbyl hydrogen dithiophosphates and sulfur-free hydrocarbyl dihydrogen phosphates and dihydrocarbyl hydrogen phosphates, said composition being at least 50% neutralized by a hydrocarbyl amine having 10 to 30 carbons in said hydrocarbyl group.
- Patent 4, 089,790 discloses an extreme-pressure lubricating oil containing (1) hydrated potassium borate, (2) an antiwear agent selected from (a) ZDDP, (b) an ester, an amide or an amine salt of a dihydrocarbyl dithiophosphoric acid or (c) a zinc alky aryl sulfonate and (3) an oil-soluble organic sulfur compound.
- U.S. Patent No. 5,076,945 discloses a lubricating oil composition containing an amine salt of a dithiobenzoic acid.
- the amines used to prepare the salts are long chain hydrocarbyl amines.
- U.S. Patents 3,849,319 and 3,951,973 describe lubricant compositions containing di- and tri(hydrocarbylammonium)trithio-cyanurates.
- the hydrocarbyl radicals include alkyl, aralkyl, aryl, alkaryl and cycloalkyl and the examples are directed to alkylamines. These lubricant compositions were stated to have improved load-carrying properties.
- WO 91/14756 describes additive compositions having utility in metal working lubrication comprising alkoxylated amine salts of dihydrocarbyldithiophosphoric acid which may be diluted with oil to form concentrates which contain from 5 to 90% by weight of the additive compositions.
- compositions which contain less phosphorous.
- This invention relates to lubricant compositions containing alkoxylated amine salts of hydrocarbylsalicylic acids, trithiocyanuric acid, hydrocarbylsulfonic acids, dihydrocarbyldithiophosphoric acids or dihydrocarbyldithiobenzoic acids having improved friction reducing properties which results in improved fuel economy In an internal combustion engines.
- salts other than those derived from dihydrocarbyldithiophosphoric acids there is the added advantage of the salts being substantially free of phosphorous which can poison the catalytic converters of cars.
- some of the salts e.g. dihydrocarbyldithiobenzoic acid derived salts have antiwear and antioxidant activity.
- the present invention therefore provides a lubricating oil composition for internal combustion engines which comprises (a) a major amount of a lubricating oil basestock and (b) a minor amount of an alkoxylated amine salt of an acid said salt having the general formula 1-.
- Z is derived from either a hydrocarbylsalicylic acid, trithiocyanuric acid, a hydrocarbylsulfonic acid, a dihydrocarbyldithiophosphoric acid or a dihydrocarbyldithiobenzoic acid and wherein R is a hydrocarbyl group having from 2 to 22 carbon atoms with the proviso that when Z is derived from a hydrocarbylsalicylic acid R is an alkyl or alkenyl group of from 6 to 18 carbon atoms and when Z is derived from a hydrocarbylsulfonic acid that R is a hydrocarbyl group of from 6 to 18 carbon atoms, x and y are each independently integers of from 1 to 15 with the proviso that the sum of x + y is from 2 to 20 and n is 1 or from 1 to 3 preferably 3 when the acid is trithiocyanuric acid and that when Z in formula I is derived from a dihydrocarbyldithi
- the invention further provides a lubricating oil composition for internal combustion engines which comprises
- the present invention provides for the use, for reducing friction and/or improving fuel economy in an internal combustion engine, of an alkoxylated amine salt having the formula (1) set forth.
- the lubricating oil will contain a major amount of a lubricating oil basestock.
- the lubricating oil basestocks are well known in the art and can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof.
- the lubricating oil basestock will have a kinematic viscosity ranging from 5 to 10,000 cSt at 40°C, although typical applications will require an oil having a viscosity ranging from about 10 to 1,000 cSt at 40°C.
- Natural lubricating oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal and shale.
- Synthetic oils include hydrocarbon oils and halo-substituted, hydrocarbon oils such as polymerized and interpolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs thereof, and the like.
- Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc.
- Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with a variety of alcohols. Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers.
- Silicon-based oils (such as the polyakyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils.
- Other synthetic lubricating oils include liquid esters of phosphorous-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.
- the lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof.
- Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
- Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
- Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties.
- Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art.
- Rerefined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
- the amine salts of the acids are prepared from the reaction of alkoxylated, preferably propoxylated or ethoxylated, most preferably ethoxylated amines with the acid.
- Preferred ethoxylated amines used to prepare amine salts have the formula where R is hydrocarbyl group of from 2 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
- the hydrocarbyl groups include aliphatic (alky or alkenyl) groups which may be substituted with hydroxy, mercapto, amino and the like and the hydrocarbyl group may be interrupted by oxygen, nitrogen or sulfur.
- the sum of x + y is preferably 2 to 15.
- Ethoxylated and/or propoxylated amines are commercially available from Sherex Chemicals under the trade name Varonic and from Akzo Corporation under the trade names Ethomeen®, Ethoduomeen®, and Propomeen®.
- Examples of preferred amines containing from 2 to 15 ethoxy groups include ethoxylated (5) cocoalkylamine, ethoxylated (2) tallowalkylamine, ethoxylated (15) cocoalkylamine and ethoxylated (5) soyaalkylamine.
- Prefered hydrocarbylsalicylic acids used to react with alkoxylated amines to form amine salts have the following formula: wherein R 1 is a hydrocarbyl group having from 2 to 30 carbon atoms preferably a hydrocarbyl group of from 2 to 26 carbon atoms.
- Such hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic groups.
- the aliphatic and alicyclic groups may be substituted with hydroxy, alkoxy, cyano, nitro and the like and the alicyclic group may contain O, S or N as hetero atoms.
- These substituted salicylic acids are commercially available or may be prepared by methods known in the art, e.g. U.S. Patent 5,023,366.
- Trithiocyanuric acid may exist in different tautomeric forms represented by formulas II, III or mixtures thereof:
- Trithiocyanuric acid is prepared by methods well known in the art. These methods involve the treatment of cyanuric chloride with sulfur nucleophiles according to the following reaction scheme: Other sulfur nucleophiles which may be employed in the above reaction scheme include sodium sulfide, thiourea and thioacetic acid.
- Prefered hydrocarbylsulfonic acids used to react with alkoxylated amines to form amine salts have the following formula: wherein R 1 is preferably a hydrocarbyl group having from 2 to 30 and most preferably having from 2 to 26 carbon atoms.
- Such hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic groups.
- the aliphatic and alicyclic groups may be substituted with hydroxy, alkoxy, cyano, nitro and the like and the alicyclic group may contain O, S or N as hetero atoms.
- These sulfonic acids are commercially available or may be prepared by methods well known in the art.
- Preferred dihydrocarbyldithiophosphoric acids used to react with alkoxylated amines to form amine salts have the following formula: wherein R 1 and R 2 are independently hydrocarbyl groups having from 3 to 30 carbon atoms, preferably 3-20 carbon atoms.
- Such hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic groups.
- the aliphatic and alicyclic groups may be substituted with hydroxy, alkoxy, cyano, nitro and the like and the alicyclic group may contain O, S or N as hetero atoms.
- dialkyldithiophosphoric acids made from mixed (85%) 2-butyl alcohol and (15%) isooctylalcohol (mixed primary and secondary alcohols).
- Dihydrocarbyldithiophosphoric acids are commercially available from Exxon Chemical Company.
- Preferred dihydrocarbyldithiobenzoic acids used to reacted with alkoxylated amines to form amine salts have the following formula: wherein R 2 to R 6 are each preferably hydrogen; a hydrocarbyl group containing from 1 to 18 carbon atoms or a hydroxy group with the proviso that at least one of R 2 to R 5 is a hydrocarbyl group, preferably an alkyl group containing 1 to 18 carbon atoms, more preferably 1 to 6 carbon atoms. R 3 and R 5 are most preferably t-butyl groups and R 4 is most preferably hydroxy.
- the hydrocarbyl groups include aliphatic (alky or alkenyl) and alicyclic groups which may be substituted with hydroxy, mercapto, amino and the like and the hydrocarbyl group may be interrupted by oxygen, nitrogen or sulfur.
- Dithiobenzoic acids may be prepared from a phenol according to the following method.
- a phenol of the formula: is dissolved in a solvent such as dimethylsulfoxide and treated under nitrogen with potassium hydroxide dissolved in a minimum of water.
- Carbon disulfide is added under nitrogen to this mixture which is maintained at about room temperature.
- the resulting reaction mixture is heated at between 25 to 100°C for 1-3 hours and then added to an acidified water solution.
- the resulting dithiobenzoic acid can be isolated by solvent extraction using, e.g. ether and the solvent evaporated.
- alkoxylated amine salts according to the present invention are prepared by methods known to those skilled in the art.
- the preparative reaction scheme is illustrated as follows: wherein R, n, x and y are defined as above.
- Approximately equimolar amounts of alkoxylated amine and acid are mixed together in an acid/base neutralization reaction.
- the amounts of acid or base may be varied to achieve the desired acid/base balance of the final amine salt.
- the lubricant oil compositions according to the present invention comprises a major amount of lubricating oil basestock and a minor amount of the alkoxylated amine salt.
- the amount of amine salt will be from 0.001 wt% to 5 wt%, based on oil basestock, except where it is derived from a dihydrocarbyldithiophosphoric acid.
- the amount of amine salt is from 0.05 wt% to 1.0 wt%.
- the lubricant oil composition comprises a major amount of lubricating basestock and typically from 0.1 to about 5 wt%, except 5.0 wt %, and most preferably from 0.5 to 2 wt% of the salt.
- the lubricant oil composition comprises a major amount of lubricating basestock and from 0.1 to 5 wt% and most preferably from 0.5 to 2 wt% of the salt.
- the amount of alkoxylated amine salt present will be an amount effective to provide reduced friction and/or improved fuel economy in internal combustion engines.
- additives known in the art may be added to the lubricating oil basestock.
- additives include dispersants, antiwear agents, antioxidants, rust inhibitors, corrosion inhibitors, detergents, pour point depressants, extreme pressure additives, viscosity index improvers, other friction modifiers, hydrolytic stabilizers and the like. These additives are typically disclosed, for example, in "Lubricant Additives” by C. V. Smalhear and R. Kennedy Smith, 1967, pp. 1-11 and in U.S. Patent 4,105,571.
- the lubricating oil composition of this invention can be used in the lubrication system of essentially any internal combustion engine, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad engines, and the like. Also contemplated are lubricating oils for gas-fired engines, alcohol (e.g., methanol) powered engines, stationery powered engines, turbines, and the like.
- alcohol e.g., methanol
- This Example illustrates the preparation of an ethoxylated amine salt of salicylic acid according to the invention.
- 114 g of ethoxylated(5)cocoalkylamine was heated to 80°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser.
- 100 g of salicylic acid having formula was added gradually to the stirred amine solution.
- the temperature rose to 104°C due to the exothermic reaction between acid and amine.
- the reaction mixture was maintained at 104°C for 1.5 hours and then cooled to room temperature.
- the ethoxylated amine salt of alkyl salicylic acid is an effective friction modifier as shown in this example.
- the Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described by S. Jahanmir and M. Beltzer in ASLE Transactions, Vol. 29, No. 3, p.425 (1985) using a force of 0.8 Newtons (1 Kg) applied to a 12.5 mm steel ball in contact with a rotating steel cylinder that has a 43.9 mm diameter.
- the cylinder rotates inside a cup containing a sufficient quantity of lubricating oil to cover 2 mm of the bottom of the cylinder.
- the cylinder was rotated at 0.25 RPM.
- the friction force was continuously monitored by means of a load transducer.
- Friction experiments were conducted with an oil temperature of 100°C. Various amounts of ethoxylated(5)cocoalkyl amine salicylate prepared in Example 1 were added to solvent 150 N. The results of BOC friction tests are shown in Table 1.
- This Example illustrates the preparation of an ethoxylated amine salt of trithiocyanuric acid according to the invention.
- 100 g of ethoxylated(5)cocoalkylamine was heated to 70°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser.
- 14 g of trithiocyanuric acid was added gradually to the stirred amine solution.
- the temperature rose to 105°C due to the exothermic reaction between acid and amine.
- the reaction mixture was maintained at 105°C for 2 hours and then cooled to room temperature.
- the ethoxylated amine salt of trithiocyanuric acid is an effective friction modifier as shown in this example.
- the Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described in Example 2 Various amounts of ethoxylated(5)cocalkylamine trithiocyanurate prepared in Example 3 were added to solvent 150 N. The results of BOC friction tests are shown in Table 2. TABLE 2 Wt% of Ethoxylated(5)Cocoalkylamine Trithiocyanurate in Solvent 150N Coefficient Of Friction 0.00 0.29 0.05 0.16 0.10 0.076 0.20 0.06 0.30 0.05 0.50 0.05 0.80 0.05 1.00 0.05
- This Example illustrates the preparation of an ethoxylated amine salt of sulfonic acid according to the invention.
- 300 g of ethoxylated(5)cocoalkylamine was heated to 60°C with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser.
- An ethoxylated(2)tallowalkylamine sulfonate salt was prepared using the same procedure from 140 g of ethoxylated(2)tallowamine and 198 g of alky sulfonic acid.
- the ethoxylated amine salt of sulfonic acid is an effective friction modifier as shown in this example.
- the Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described in Example 2.
- Various amounts of ethoxylated(5)cocoalkyl amine alkylsulfonate prepared in Example 5 were added to solvent 150 N.
- the results of BOC friction tests are shown in Table 3.
- Example 6 The procedure of Example 6 was repeated except that ethoxylated(2)tallowalkylamine was substituted for ethoxylated(5)cocoalkylamine in the sulfonate salt.
- the results are shown in Table 4.
- TABLE 4 Wt% of Ethoxylated(5)tallowalkylamine Alkyl Sulfonate in Solvent 150N Coefficient Of Friction 0.0 0.32 0.1 0.20 0.2 0.17 0.3 0.13 0.5 0.10 0.8 0.07 1.0 0.06
- the Sequence VI High Temperature Rapid Screen Test is a shortened version of the actual ASTM Sequence VI test for fuel economy. Although it uses the same engine as the Sequence VI, only the high temperature phase of the test is run. This emphasizes the boundary lubrication regime which basically determines the fuel economy capability of the additive.
- the test procedure is outlined below: Step # Test Sequence Time 1 Cool down/warm up 20 min 2 Detergent Flush to Candidate Oil 1 hr, 20 min 3 Stabilize Step 1 - Stage 275°F 2 hr 4 BSFC Measurement Step 1 - Stage 275°F 30 min 5 Stabilize Step 2 - Stage 275°F 2 hr 6 BSFC Measurement Step 2 - Stage 275°F 30 min
- Each candidate oil run is preceded by a flush oil run to ensure that any "carry-over" effect is eliminated.
- the fuel economy of the candidate oil as measured by brake specific fuel consumption (BSFC), is measured twice in the experiment. Once after a two hour stabilization, or break-in period, and then again after another two hour stabilization period.
- a base oil is run periodically throughout the test to determine the test precision. In this particular test the base oil was a commercially available SAE 5W-30 oil. The results are shown in the following table.
- ethoxylated (5) cocoalkylamine 140 g was placed in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser. The ethoxylated amine was stirred and heated to 50°C. A stoichiometic amount of 4-hydroxy-3, 5-ditertiary-butyldithiobenzoic acid (100g) was then slowly added into the warm ethoxylated amine solution with stirring. The temperature was raised to 95°C for 2 hours. The neutralization reaction was controlled with a portable pH meter. The addition of the acid was stopped at pH 7. After 2 hours of stirring at 95°C, the reaction product was cooled to room temperature and used without further purification.
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Applications Claiming Priority (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/021,292 US5320766A (en) | 1993-02-22 | 1993-02-22 | Lubricant composition containing alkoxylated amine salt of a dihydrocarbyldithiophosphoric acid |
US21292 | 1993-02-22 | ||
US08/021,295 US5320767A (en) | 1993-02-22 | 1993-02-22 | Lubricant composition containing alkoxylated amine salt of hydrocarbylsulfonic acid |
US21505 | 1993-02-22 | ||
US21509 | 1993-02-22 | ||
US08/021,294 US5330666A (en) | 1993-02-22 | 1993-02-22 | Lubricant composition containing alkoxylated amine salt of hydrocarbylsalicyclic acid |
US21295 | 1993-02-22 | ||
US08/021,509 US5308518A (en) | 1993-02-22 | 1993-02-22 | Lubricant composition containing alkoxylated amine salt of a dihydrocarbyldithiobenzoic acid |
US08/021,505 US5275745A (en) | 1993-02-22 | 1993-02-22 | Lubricant composition containing alkoxylated amine salt of trithiocyanuric acid |
PCT/EP1994/000521 WO1994019434A1 (en) | 1993-02-22 | 1994-02-22 | Lubricant composition containing alkoxylated amine salts of acids |
US21294 | 2004-12-23 |
Publications (2)
Publication Number | Publication Date |
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EP0684978A1 EP0684978A1 (en) | 1995-12-06 |
EP0684978B1 true EP0684978B1 (en) | 1997-05-21 |
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Application Number | Title | Priority Date | Filing Date |
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EP94909034A Expired - Lifetime EP0684978B1 (en) | 1993-02-22 | 1994-02-22 | Lubricant composition containing alkoxylated amine salts of acids |
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EP (1) | EP0684978B1 (ja) |
JP (1) | JPH09504040A (ja) |
CA (1) | CA2156608A1 (ja) |
DE (1) | DE69403322T2 (ja) |
WO (1) | WO1994019434A1 (ja) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5352374A (en) * | 1993-02-22 | 1994-10-04 | Exxon Research & Engineering Co. | Lubricant composition containing alkoxylated amine salt of a dihydrocarbyldithiophosphoric acid (law024) |
CN1045103C (zh) * | 1994-06-18 | 1999-09-15 | 兰州炼油化工总厂三星公司 | 一种烷基水杨酸盐润滑油添加剂 |
US8343901B2 (en) | 2010-10-12 | 2013-01-01 | Chevron Oronite Company Llc | Lubricating composition containing multifunctional hydroxylated amine salt of a hindered phenolic acid |
US8334242B2 (en) | 2010-10-12 | 2012-12-18 | Chevron Oronite Company Llc | Lubricating composition containing multifunctional borated hydroxylated amine salt of a hindered phenolic acid |
CA2822351C (en) * | 2010-12-21 | 2019-10-29 | The Lubrizol Corporation | Lubricating composition containing an antiwear agent |
CN107109279B (zh) | 2014-10-31 | 2020-12-25 | 巴斯夫欧洲公司 | 润滑剂组合物中的烷氧基化酰胺、酯和抗磨剂 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4382006A (en) * | 1979-11-06 | 1983-05-03 | Mobil Oil Corporation | Friction reduction additives and compositions thereof |
US5080813A (en) * | 1990-03-26 | 1992-01-14 | Ferro Corporation | Lubricant composition containing dialkyldithiophosphoric acid neutralized with alkoxylated aliphatic amines |
CA2097326A1 (en) * | 1990-12-27 | 1992-06-28 | Jacob Joseph Habeeb | Smoke reducing additives for two-cycle engine lubricant-fuel mixture |
-
1994
- 1994-02-22 WO PCT/EP1994/000521 patent/WO1994019434A1/en active IP Right Grant
- 1994-02-22 DE DE69403322T patent/DE69403322T2/de not_active Expired - Fee Related
- 1994-02-22 JP JP6518668A patent/JPH09504040A/ja active Pending
- 1994-02-22 EP EP94909034A patent/EP0684978B1/en not_active Expired - Lifetime
- 1994-02-22 CA CA002156608A patent/CA2156608A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
CA2156608A1 (en) | 1994-09-01 |
EP0684978A1 (en) | 1995-12-06 |
DE69403322T2 (de) | 1997-10-16 |
DE69403322D1 (de) | 1997-06-26 |
JPH09504040A (ja) | 1997-04-22 |
WO1994019434A1 (en) | 1994-09-01 |
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